Covalent connections between metal–organic frameworks and polymers including covalent organic frameworks

Abstract

Hybrid composite materials combining metal–organic frameworks (MOFs) and polymers have emerged as a versatile platform for a broad range of applications. The crystalline, porous nature of MOFs and the flexibility and processability of polymers are synergistically integrated in MOF–polymer composite materials. Covalent bonds, which form between two distinct materials, have been extensively studied as a means of creating strong molecular connections to facilitate the dispersion of “hard” MOF particles in “soft” polymers. Numerous organic transformations have been applied to post-synthetically connect MOFs with polymeric species, resulting in a variety of covalently connected MOF–polymer systems with unique properties that are dependent on the characteristics of the MOFs, polymers, and connection modes. In this review, we provide a comprehensive overview of the development and strategies involved in preparing covalently connected MOFs and polymers, including recently developed MOF–covalent organic framework composites. The covalent bonds, grafting strategies, types of MOFs, and polymer backbones are summarized and categorized, along with their respective applications. We highlight how this knowledge can serve as a basis for preparing macromolecular composites with advanced functionality.